EP4200464A1 - Appareil et procédé pour effectuer une électrolyse - Google Patents

Appareil et procédé pour effectuer une électrolyse

Info

Publication number
EP4200464A1
EP4200464A1 EP21766621.3A EP21766621A EP4200464A1 EP 4200464 A1 EP4200464 A1 EP 4200464A1 EP 21766621 A EP21766621 A EP 21766621A EP 4200464 A1 EP4200464 A1 EP 4200464A1
Authority
EP
European Patent Office
Prior art keywords
electrolyte
electrolysis
electrolytic cell
electrode
stripping
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP21766621.3A
Other languages
German (de)
English (en)
Inventor
Oliver GOLTZ
Rainer SIEBEN
Andreas Bulan
Michael Grossholz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Covestro Deutschland AG
Original Assignee
Covestro Deutschland AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Covestro Deutschland AG filed Critical Covestro Deutschland AG
Publication of EP4200464A1 publication Critical patent/EP4200464A1/fr
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/02—Process control or regulation
    • C25B15/023—Measuring, analysing or testing during electrolytic production
    • C25B15/025—Measuring, analysing or testing during electrolytic production of electrolyte parameters
    • C25B15/029—Concentration
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/34—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/02—Process control or regulation
    • C25B15/023—Measuring, analysing or testing during electrolytic production
    • C25B15/025—Measuring, analysing or testing during electrolytic production of electrolyte parameters
    • C25B15/027—Temperature
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • C25B15/085—Removing impurities
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • C25B15/087—Recycling of electrolyte to electrochemical cell
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/05—Pressure cells
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/13—Single electrolytic cells with circulation of an electrolyte
    • C25B9/15—Flow-through cells
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/70—Assemblies comprising two or more cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Definitions

  • the invention relates to a device and a method for operating an electrolysis with an alkali metal hydroxide solution originally containing oxygen as the electrolyte precursor, in which the pressure, temperature of the alkali metal hydroxide solution and its CL quantity are adjusted in each case.
  • Oxygen-containing aqueous alkali hydroxide solution hereinafter also referred to as lye, such as caustic soda or potassium lye, are produced or used in chlor-alkali electrolysis with oxygen-depleted cathodes (SVK) or alkaline water electrolysis. Oxygen gas is present in dissolved or solvated form in these oxygen-containing aqueous alkali metal hydroxide solutions.
  • lye oxygen-depleted cathodes
  • Oxygen gas is present in dissolved or solvated form in these oxygen-containing aqueous alkali metal hydroxide solutions.
  • thermoplastics such as polypropylene (also referred to as PP in the following) (e.g. PP2222 or PP2250), PVC or PTFE are usually used for lye-contacted materials.
  • PP2222 or PP2250 polypropylene
  • PTFE polypropylene
  • C-PVC C-PVC
  • a thermoplastic material is preferred as the material
  • plastic materials in devices for electrolysis are their electrical insulating effect.
  • Metallic materials such as nickel, which can be used, entail a great deal of electrical insulation work.
  • Metallic materials are also not corrosion-proof under every potential. Since stray currents and potential transfers can also occur during electrolysis, preference should therefore be given to plastic-based materials.
  • polypropylene is preferably used for parts of the plant that come into contact with caustic.
  • Polypropylene is resistant to aqueous solutions of inorganic salts and almost all inorganic acids and bases, even in high concentrations and at temperatures above 60°C.
  • PP such as hexagonal crystalline polypropylene.
  • various high-molecular polypropylenes such as e.g. B. homopolymers (PP-H, type 1) and random copolymers (PP-R, type 3) are used.
  • hexagonal ß-crystalline PP-H is produced by special nucleation and optimal processing. This material meets all the requirements of international standards for PP homopolymers.
  • piping systems are aqueous solutions, acids, alkalis and solvents.
  • the degree of chemical resistance of the polypropylene can be influenced by the pigmentation and by the homogeneity and structure of the crystalline phase (Schöpf, A., Schneider, H.: Polypropylene for piping systems, plastics, 87 (1997) 2, pp. 198-201 ).
  • thermoplastic material in particular the PP material, must be processed, i.e. usually welded, which can result in structural changes and also influences from additives in the welding material in the plastic.
  • the system availability for technical chlorine systems should be more than 2 years, preferably more than 4 years.
  • Electrolysis devices that use oxygen gas in a half-cell reaction usually contain at least one so-called gas diffusion electrode, through which oxygen-containing gas can be supplied as a reactant to the half-cell. Electrolysis devices that release oxygen gas in a half-cell reaction are used, for example, for the electrolysis of water, the so-called alkaline water electrolysis. In both cases, gaseous oxygen is introduced at at least one electrode into the electrolyte in contact with said electrode as an electrolyte by the electrochemical process taking place at this electrode.
  • the object was therefore to provide an electrolysis process and a corresponding device, in which the service life of a plastic used as the material of the electrolysis device of the parts of the device that come into contact with the lye is increased. It should still like This ensures that the system is economical to operate and manufacture, that the plastic used is easy to process and that an efficient electrolysis process is guaranteed.
  • This above-mentioned object was achieved by adjusting the oxygen content of the aqueous alkali metal hydroxide solution to be fed into the half-cell as the electrolyte, as well as its pressure in the feed system of the electrolyzer.
  • a first object of the invention is therefore a method for operating an electrolysis, in which gaseous oxygen is introduced into the electrolyte in contact with said electrode on at least one electrode by the electrochemical process taking place on said electrode, characterized in that said electrolyte in the electrolytic cell is introduced and led out again and said electrolyte to be introduced into the electrolytic cell is an alkaline, aqueous electrolyte containing alkali hydroxide and at an absolute pressure of 1 bar and a temperature of 20°C a quantity of Cb between 0 and 25 mg/L, with the introduction into the electrolytic cell, the absolute pressure of the electrolyte to be introduced is in the range of 1.2 bar to 3.5 bar and the temperature of the electrolyte to be introduced is greater than 40°C.
  • a sample of the electrolyte to be determined is taken, stored in a nitrogen or argon atmosphere and cooled to 20.degree.
  • the Oz quantity is then determined as described below. Storage under nitrogen or argon ensures that no Cb can escape or be absorbed. Uptake would be possible through contact with air, since O2 solubility increases, particularly when the sample cools, and Oz could be absorbed.
  • the amount of O2 in the electrolyte can be determined by means of optical oxygen measurement using fluorescence quenching methods (for example using the SE 740-Memosens® Oxygen Sensor from Knick Electronic Measuring Devices GmbH & Co. KG). Furthermore, other sensors or the measurement of the redox potential can also be used as methods for determining the amount of dissolved O. All determinations of the O2 quantities carried out within the scope of the present application were carried out using fluorescence quenching methods. Unless otherwise stated, the measurement was carried out on samples taken at a temperature of 20° C. and an absolute pressure of 1 bar.
  • An electrolytic cell usually contains a cathode half-shell with a cathode, a catholyte inlet, at least one catholyte outlet, and further containing an anode half-shell, the anode half-shell having at least one anolyte inlet for introducing an anolyte and one Anolyte outlet and an anode, and a separator arranged between the anode half-shell and the cathode half-shell for separating the anode compartment and the cathode compartment, further containing electrical power lines for connecting the anode and cathode to a DC voltage source.
  • electrolytic cells and electrolyzers with a large number of electrolytic cells are necessary in order to produce industrial quantities of product using electrolysis methods.
  • technical production quantities are understood to mean product quantities of more than 0.1 kg/(h*m 2 ) per electrolytic cell.
  • electrolytic cells with an electrode area of more than 2m 2 per electrolytic cell are usually used for this purpose.
  • the electrolysis cells are combined in groups of up to 100 pieces in an electrolysis rack. Several frames with electrolytic cells then form an "electrolyser".
  • the capacity of an industrial electrolyser for example in chlorine production, is currently up to 30,000 t/a of chlorine and the respective equivalents of caustic soda and possibly hydrogen.
  • the electrolyte to be introduced into the electrolytic cell (also “electrolyte to be introduced”) is defined as the electrolyte that is used immediately before it is introduced into the electrolytic cell and used in the electrolytic cell for the electrochemical process at the electrode.
  • the electrolyte to be introduced is an alkaline, aqueous electrolyte containing alkali metal hydroxide and, at an absolute pressure of 1 bar and a temperature of 20° C., an amount of Cb of between 0 and 25 mg/L.
  • a parameter range is defined that lies between two range limits, these range limits are of course not included in the parameter range. Conversely, when a parameter range is defined as being from one boundary to the other, the range boundaries are included in the parameter range.
  • a method is characterized in that said electrolyte flows through the electrolytic cell and for this purpose electrolyte is continuously introduced into the electrolytic cell and fed out again.
  • electrolyte to be introduced is introduced continuously, ie simultaneously, into the electrolytic cell and electrolyte that has been carried out is carried out again.
  • the electrolyte to be introduced is pressurized in the method according to the invention for introduction into the electrolytic cell, preferably for continuous introduction into the electrolytic cell, for example with the aid of a pump, and has an absolute pressure before entering the electrolytic cell in the range from 1.2 bar to 3.5 bar.
  • the area of an electrolysis device suitable for the process, which is used to feed in the electrolyte to be introduced, is referred to by the person skilled in the art as the infeed system or “feed system”.
  • the feed system of an electrolysis device suitable for the process includes the storage container for the electrolyte, electrolyte-carrying pipelines and the necessary control valves and shut-off valves, the electrolyte distributor, pumps, filters, heat exchangers and various data acquisition devices such as flow meters or temperature and pressure sensors.
  • the task of the feed system is to evenly and homogeneously distribute the electrolyte to be fed in to all electrolytic cells in the electrolyser.
  • the pressure of the electrolyte to be introduced (preferably generated by a pump) must be higher than the ambient pressure (atmospheric pressure), i.e. at least 1.2 bar, so that all electrolysis cells have a sufficient amount of to be fed in Electrolytes can be supplied.
  • a pressure is in turn preferably built up after the removal of the electrolyte from the storage container and thus prevails in the feed system between the pressure build-up device downstream of the storage container, preferably pump and electrolytic cell.
  • the amount of electrolyte to be introduced used for the process according to the invention is preferably between 100 and 900 L/h per electrolytic cell.
  • a volume flow of the electrolyte to be introduced of 18 m 3 /h to 162 m 3 /h is preferred via the feed system for distributing the electrolyte to be introduced into the electrolysis cells.
  • the absolute pressure of the electrolyte to be introduced in the feed system is up to 3.5 bar.
  • a preferred method according to the invention is characterized in that said electrolyte to be introduced is in contact with at least one thermoplastic material at the supply lines and/or the inlet to the electrolytic cell, preferably selected from polypropylene (PP), polyvinyl chloride (PVC) or polytetrafluoroethylene (PTFE) .
  • PP polypropylene
  • PVC polyvinyl chloride
  • PTFE polytetrafluoroethylene
  • said electrolyte to be introduced has a temperature of at least 40°C, preferably in the range from 60°C to 85°C.
  • Electrolyte (also “expelled electrolyte”) is defined as the electrolyte that is led out of the electrolytic cell and is immediately used on the electrode after use for the electrochemical process exits the electrolytic cell. If the electrolysis device used to carry out the method according to the invention contains more than one electrolysis cell in an electrolyzer, the electrolyte removed from the individual electrolysis cells can first be combined in an electrolyte collector and then discharged from the electrolyzer.
  • said electrolyte to be introduced has a smaller amount of Cb than the electrolyte carried out.
  • the said discharged electrolyte has a Cb amount of at least 25 mg/L, preferably at least 30 mg/L, very particularly preferably at least 35 mg/L.
  • Methods which are preferred according to the invention are characterized in that said at least one electrode consumes oxygen gas (oxygen-consuming cathode) or develops oxygen as a result of the electrochemical process taking place there.
  • At least one oxygen-consuming cathode is preferably used in the method according to the invention.
  • the method according to the invention can be operated as a sodium chloride electrolysis using at least one oxygen-consuming cathode (SVK) (in short: NaCl-SVK electrolysis).
  • SVK oxygen-consuming cathode
  • the basic principle of NaCl-SVK electrolysis can be found in the literature: e.g. Moussalem et.al. J. Appl. Electrochem., 38(9), 1177-1194 (2008).
  • the alkaline, aqueous electrolyte (catholyte) used is, for example, a sodium hydroxide solution.
  • this is preferably carried out in such a way that the electrolyzer is supplied with a dilute lye, preferably caustic soda, with a concentration in the range from 28 to 31% by weight as the electrolyte to be introduced, and the electrolyser is supplied with a comparative electrolyte as the discharged electrolyte lye with a concentration in the range from 28.5 to 38% by weight is removed again in relation to the electrolyte to be introduced.
  • the alkaline, aqueous electrolyte (anolyte) used is, for example, an aqueous solution of potassium hydroxide (potassium hydroxide).
  • potassium hydroxide potassium hydroxide
  • This is preferably performed in the embodiment as alkaline water electrolysis so that the electrolyzer as an electrolyte to be introduced Diluted lye, preferably potassium lye, with a concentration in the range from 20 to 28% by weight, and fed to the electrolyser as the electrolyte carried out, a lye with a higher concentration than the electrolyte to be introduced, with a concentration in the range from 20.5 to 33% by weight is removed again.
  • the temperature of the electrolyte to be introduced is preferably between 60 and 88°C for the method according to the invention and is adjusted by the temperature and the volume flow in such a way that the electrolyte that is fed out has a temperature of 85 to 95°C.
  • the aim is to have as high a temperature as possible and as low a lye concentration as possible in the electrolyte that is fed out.
  • gaseous oxygen is supplied to the cathode as a reactant in NaCLSVK electrolysis, or oxygen gas is generated at the anode in water electrolysis, for example, and the gaseous oxygen comes into intensive contact with the alkaline, aqueous electrolyte containing alkali hydroxide during electrolysis, the The electrolyte discharged from the electrolytic cell has a higher oxygen content than the amount of O2 of up to 40 mg/L. Consequently, during the operation of the electrolysis, gaseous oxygen is carried into the electrolyte and absorbed (particularly dissolved or solvated), thereby increasing the amount of O2 present in the electrolyte.
  • the electrolyte removed from the electrolyser is discharged into a storage tank via an electrolyte collector and another pipeline, if necessary with shut-off valves and measuring device for flow.
  • Part of the lye is removed, particularly in the case of NaCLSVK electrolysis, and supplied for sale or to a consumer; if necessary, the concentration is increased in each case by evaporation.
  • the remainder is diluted with water in the NaCLSVK electrolysis and fed to the electrolysis via the feed system. In this case, only a partial flow can be routed via a heat exchanger so that the inlet temperature of the liquor required for the electrolyser is reached.
  • the electrolyte that is present in the storage container during operation preferably has an O2 quantity of between 0 and 25 mg O2/L electrolyte, measured at an absolute pressure of 1 bar and a temperature of 20°C.
  • the electrolyte from the storage tank is returned to the electrolytic cells via the feed system.
  • the pump conveys the electrolyte to be introduced with an absolute pressure in the feed system of between 1.2 and 3.5 bar to the electrolytic cells.
  • the pressure can be set accordingly, for example, by dimensioning the cross-section of the pipelines of the feed system in such a way that the absolute pressure in the feed system assumes the desired value.
  • the absolute pressure of the electrolyte to be introduced is preferably from 1.2 to 3.5 bar, particularly preferably from 1.2 to 3.0 bar, more preferably from 1.4 to 3.0 bar, very particularly preferably from 1.4 to 2.5 bar.
  • An embodiment of the method according to the invention is characterized in that electrolyte is subjected to a step of reducing the amount of Cb before it is introduced into the electrolytic cell and is then introduced into the electrolytic cell as said electrolyte to be introduced.
  • the electrolyte led out of the at least one electrolytic cell is first transferred to the storage tank and the reduction of the Cb quantity from the electrolyte is only carried out before it is used from the storage tank for reuse and introduced into the electrolytic cell as the electrolyte to be introduced.
  • electrolyte that has been removed is subjected to at least one step of reducing the amount of Cb after it has been discharged and is then reused to provide electrolyte to be introduced into the electrolytic cell.
  • the device parts of the pipeline and storage tank can also be used longer if plastic materials are used for the pipelines or storage tanks that come into contact with electrolyte.
  • the electrolyte fed out of the at least one electrolytic cell is preferably subjected to a reduction in the amount of Cb, as described above.
  • the electrolyte should preferably have a Cb quantity of between 0 and 25 mg/L after the oxygen reduction at an absolute pressure of 1 bar and a temperature of 20°C. This reduction in oxygen particularly preferably takes place before the electrolyte that is fed out is transferred to the storage tank.
  • the success of the stripping can be monitored by measuring the amount of Cb in the electrolyte discharged from the stripper.
  • At least water is added to the discharged electrolyte before the step of reducing the amount of Cb in order to reduce the alkalinity. It is in turn preferred if the alkali metal hydroxide concentration of the discharged electrolyte is adjusted to a concentration in the range from 28 to 31% by weight by adding at least water before the step of reducing the amount of Cb. If the method according to the invention is carried out as part of a NaCl-SVK electrolysis, the electrolyte (catholyte) carried out on the cathode side of the electrolytic cell is subjected to a step of reducing the O2 quantity.
  • the O2 amount can be reduced by at least one step selected from
  • the oxygen reduction it is preferred according to the invention, for the oxygen reduction, to subject the discharged electrolyte to at least one stripping with an inert gas as stripping gas, preferably with at least one inert gas selected from nitrogen, argon or mixtures thereof as stripping gas.
  • an inert gas as stripping gas
  • stripping to mean desorption of the oxygen (O2) dissolved in the discharged electrolyte, which is at least partially brought about by contact with at least one stripping gas, with a reduction in the amount of Ch in the electrolyte.
  • an inert gas to be a gas which, under the conditions of use in the process according to the invention, undergoes almost no chemical reaction (that is to say no more chemical reactions compared to nitrogen as the reference gas) and which is different from oxygen.
  • the preferred volume flow of the electrolyte onto the stripping device used for the oxygen reduction is from 16 m 3 /h to 160 m 3 /h.
  • the amount of stripping gas used per 750 L of electrolyte is preferably between 0.01 and 1 m 3 .
  • the preferred temperature of the electrolyte fed to the stripping device is from 20 to 85.degree.
  • Nitrogen is preferably used as the stripping gas.
  • the preferred residence time of the stripping gas is from 20 to 120 seconds.
  • the absolute pressure in the stripping device is between 0.6 and 1.2 bar during the stripping process.
  • stripping device that can be used according to the invention for oxygen reduction can preferably be constructed from at least one material selected from thermoplastics (such as preferably PP or PP GRP), rubberized steel or combinations thereof.
  • the stripping device that can be used for oxygen reduction has at least one space for stripping, into which both the electrolyte, preferably the electrolyte carried out, and at least one stripping gas can be introduced and contacted with one another, and used stripping gas and stripped electrolyte can be removed.
  • a stripping room whose height is greater than its width and length is also referred to as a stripping column.
  • a stripping column is preferably provided from a closed empty tube which contains at least said inlets and outlets for the electrolyte, the stripping gas, the used stripping gas and the stripped electrolyte.
  • the stripper used for the oxygen reduction process step has at least one, preferably cylindrical, stripping space with a base area of 0.3 m 2 to 1.2 m 2 and a height of 1 m to 3 m. on, in which both the electrolyte, preferably the electrolyte led out, and at least one stripping gas can be introduced and contacted with one another.
  • the inlet in particular in the form of nozzles, a coil or a perforated plate, through which the stripping gas is supplied, is located at the lower end of the space for stripping.
  • the electrolyte can have an inlet for the electrolyte at the upper end of the space for stripping or at the lower end of the space for stripping, the inlet for the electrolyte preferably being at the upper end of the space for stripping, in particular above the nozzles for supplying the stripping gas, located.
  • FIG. 4 An example of a stripper in the form of a stripping column with an electrolyte inlet and a stripping gas inlet, each at the lower end of the space for stripping, is illustrated in FIG.
  • stripping gas and electrolyte are conducted through the stripping column in cocurrent.
  • the electrolyte fed out of the at least one electrolysis cell of the electrolyzer 50 is combined in the electrolyte collector 13 and fed from there to a stripping column 40 from below.
  • the stripping column 40 comprises an empty tube with an overflow, from which the liquor supplied from below can run off. During operation, the stripping column is filled with electrolyte between the inlet and outlet.
  • the stripping gas 41 is carried out via a gas distributor 46, for example in the form of a pipe system in a serpentine form, or is supplied to a perforated plate or via one or more nozzles from below and runs upwards in cocurrent with the liquor.
  • the stripping gas leaves the stripping column 40 above the electrolyte outlet 42 and can be fed to an exhaust air treatment. Nitrogen is preferably used as the stripping gas 41 .
  • the liquor 40a depleted in CL is fed to a storage container or back to the electrolyzer 50, for example.
  • Stripping gas and electrolyte are very particularly preferably conducted in countercurrent in the stripper.
  • the inlet for the electrolyte is preferably at the upper end of the space for stripping, in particular above the nozzles for supplying the stripping gas, and the outlet for the stripped electrolyte is at the lower end of the space for stripping and the Outlet of the gas formed from the stripping gas after stripping is located at the upper end of the space for stripping.
  • FIG. 1 A preferred embodiment of a stripping device which can be used in the process according to the invention in the form of a countercurrent stripping column is disclosed in FIG. In this arrangement, stripping gas and electrolyte are fed through the stripping column in countercurrent.
  • the electrolyte fed out of the at least one electrolysis cell 5 of the electrolyzer 50 is combined in the electrolyte collector 13 and fed from there to a stripping column 40 from above.
  • the stripping column 40 comprises an empty pipe with an electrolyte outlet at the bottom, from which the electrolyte supplied from above can run off after stripping.
  • the stripping column 40 is filled with electrolyte between the electrolyte inlet, which can take place, for example, via a liquid distributor 45, and the electrolyte outlet, from which the low-CL lye 40a is discharged.
  • the stripping gas 41 is fed to the column from below via a gas distributor 46, e.g. a pipe system consisting of e.g.
  • the used stripping gas 42 leaves the stripping column above the electrolyte feed and can be fed to an exhaust air treatment. Nitrogen is preferably used as the stripping gas.
  • packing can be contained in the stripping chamber of the stripper, as shown in FIG.
  • structured packings such as are known from distillation technology can be used.
  • the stripper is equipped with at least one packing in the stripping area, selected from spherical packing with network structures or other recesses and geometries, cylindrical rings such as Raschig rings, hollow cylinders, halved hollow bodies or other customary embodiments.
  • the filling bodies can be made of different materials, e.g. As nickel, nickel-plated, stainless steel, plastic or ceramic.
  • FIG. 5 A preferred embodiment of a stripping device which can be used in the process according to the invention according to FIG. 5 in the form of a stripping column equipped with a packing is disclosed in FIG.
  • the electrolyte fed out of the at least one electrolysis cell 5 of the electrolyzer 50 is combined in the electrolyte collector 13 and fed from there to a stripping column 40 from above.
  • the stripping column comprises an empty tube which is filled with random packings 44, e.g. Raschig rings or packings, as are known from distillation technology.
  • the stripping column is equipped with a drain at the bottom, from which the electrolyte fed in from above can drain off after stripping.
  • the supplied electrolyte can be applied to the filling bodies via a liquid distributor 45 . During operation, the stripping column is not completely filled with electrolyte between the inlet and the outlet.
  • the stripping gas 41 is supplied from below, this can preferably also be carried out from below via a gas distributor 46 such as a pipe system, e.g.
  • the used stripping gas 42 leaves the stripping column above the electrolyte feed.
  • the stripped electrolyte 40a leaves the column below the stripping gas inlet. Nitrogen is preferably used as the stripping gas 41 .
  • the electrolyte (catholyte) carried out on the cathode side of the electrolytic cell is stripped, in particular using at least one stripping column (in particular according to a stripping column according to one of Figs. 4, 5 or 6) subject.
  • the electrolyte collector in FIGS. 4, 5 and 6 would be referred to as a catholyte collector.
  • a further object of the invention is therefore an electrolysis device containing (a) at least one electrolyzer containing
  • At least one electrolytic cell containing at least one electrode suitable for an electrochemical process in which oxygen gas is introduced into the electrolyte of the electrolyser in contact with said electrode
  • the electrolyte to be introduced • at least one inlet for the introduction of electrolyte to be introduced with a feed line at least into said at least one electrolytic cell, the electrolyte to be introduced containing an amount of Cb of between 0 and 25 mg/L and an absolute pressure of 1.2 bar to 3.5 bar ( abs.) and has a temperature of more than 40°C,
  • At least one device for reducing the amount of Cb of aqueous alkaline liquids to provide the electrolyte to be introduced which device is in fluid communication with the at least one inlet for the introduction of electrolyte to be introduced.
  • An electrolyzer as shown in FIG. 2 or FIG. 3, is particularly suitable.
  • a pump for example, can be used as a device for increasing the pressure.
  • the electrolysis device also includes a storage container for electrolytes.
  • the storage container can contain at least one inflow which is in fluid connection with the device for reducing the amount of Cb, wherein the device for reducing the amount of Cb is in fluid connection with the outlet for removing discharged electrolyte. In this way, the device reduces the oxygen content of the discharged electrolyte before it is introduced into the reservoir.
  • the reservoir can contain at least one outlet for the discharge of electrolyte, which is in fluid connection with the device for increasing the pressure, the latter in turn being in fluid connection with at least one inlet for the introduction of electrolyte to be introduced with a feed line at least into said at least one electrolysis cell.
  • the electrolysis device preferably contains a heat exchanger, which in turn is particularly preferably located between the inlet for the introduction of electrolyte to be introduced and the device for increasing the pressure (eg pump) of the electrolyte removed from the storage container. Between the heat exchanger and the inlet for the introduction of electrolyte to be introduced, there can again be a filter through which the electrolyte can be passed before introduction.
  • Embodiments individually or in combination are also preferred for the device, provided they are features of the device. Examples include:
  • a preferred electrolysis device is characterized in that said at least one electrode, in particular the electrode 7, is an oxygen-consuming cathode.
  • said at least one electrode in particular the electrode 7, is an oxygen-consuming cathode.
  • the electrolysis device according to the invention preferably contains electrolyte to be introduced (in particular electrolyte 8 to be introduced), which is an alkaline, aqueous electrolyte containing alkali hydroxide and an amount of Cb of between 0 and 25 mg/L.
  • Electrode suitable for an electrochemical process in which oxygen gas is introduced into the electrolyte in contact with said electrode
  • Fig. 1 shows the electrolyte supply and discharge as an electrolyte circuit on an electrolyzer
  • FIG. 2 shows an example of an electrolysis device according to the invention with a device for Cb reduction in the electrolyte, preferably designed as a stripping column.
  • At least one electrolytic cell (5) containing at least one electrode (7) suitable for an electrochemical process in which oxygen gas is introduced into the electrolyte of the electrolyser (50) in contact with said electrode,
  • At least one device (40) for reducing the Cb amount of aqueous, alkaline liquids to provide the electrolyte (8) to be introduced which is in fluid communication with the at least one inlet (1c) for the introduction of electrolyte (8) to be introduced.
  • FIG. 3 shows an example of an electrolysis device according to the invention for water electrolysis, the electrolysis device containing a device for Cb reduction in the electrolyte, preferably designed as a stripping column.
  • 4 shows the integration of a stripping column as a device for O2 reduction 40 into the electrolysis device, the stripping column 40 being designed in such a way that stripping gas 41 and electrolyte are conducted in cocurrent.
  • FIG. 5 shows the integration of a stripping column as a device for O2 reduction 40 into the electrolysis device, the stripping column being designed in such a way that stripping gas 41 and electrolyte are conducted in countercurrent.
  • FIG. 6 shows the integration of a stripping column as a device for O2 reduction 40 into the electrolysis device, the stripping column being designed in such a way that stripping gas 41 and electrolyte are conducted in countercurrent and the stripping column 40 is filled with random packing 44 .
  • Each electrolysis cell was supplied with an average of approx. 250 L/h caustic soda, the total caustic volume flow to the electrolyzer was 39.5 m 3 /h.
  • the absolute pressure of the electrolyte in the feed system was 4 bar and the temperature of the lye was 70°C.
  • the CL quantity of the electrolyte to be introduced in the feed system was 28 mg/L.
  • the O2 quantity of the discharged electrolyte behind the electrolyser was 39 mg/L caustic soda, measured with the measuring probe SE 740-Memosens® Oxygen Sensor from Knick Electronic Measuring Devices GmbH & Co. KG.
  • the concentration of the discharged electrolyte was 31.5% by weight in the outlet of the electrolyser.
  • the first material changes to the weld seams of the PP used were observed during a routine inspection. After 2 years of operation, the first leaks in the weld seams and extensive abrasion of the PP were observed, so that the first pipe sections had to be replaced and the container linings had to be renewed.
  • the operating time per year was approx. 8600 hours.
  • the electrolyzer from Example 1 was charged in the same way, but the O2 quantity of the electrolyte to be introduced in the feed was 20 g/L.
  • the absolute pressure of the electrolyte in the feed system was 1.4 bar due to the enlargement of the pipe cross-sections and the use of valves with a lower pressure loss.
  • the electrolyte discharged from the electrolyzer was fed to a stripper.
  • the stripper was charged from above with electrolyte that had been carried out at a volume flow rate of 113 m 3 /h.
  • a stripper was made of PP reinforced with GRP.
  • the stripper was designed as an empty pipe with a diameter of 90 cm and a filling height of 200 cm.

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  • Chemical & Material Sciences (AREA)
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  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Automation & Control Theory (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

L'invention concerne un appareil et un procédé pour effectuer une électrolyse avec une solution d'hydroxyde alcalin contenant initialement de l'oxygène comme précurseur d'électrolyte, la pression et la température de la solution d'hydroxyde alcalin ainsi que sa teneur en O2 étant définies.
EP21766621.3A 2020-08-24 2021-08-24 Appareil et procédé pour effectuer une électrolyse Pending EP4200464A1 (fr)

Applications Claiming Priority (2)

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EP20192385.1A EP3960903A1 (fr) 2020-08-24 2020-08-24 Dispositif et procédé de fonctionnement d'une électrolyse
PCT/EP2021/073327 WO2022043290A1 (fr) 2020-08-24 2021-08-24 Appareil et procédé pour effectuer une électrolyse

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JP5437968B2 (ja) * 2010-10-14 2014-03-12 本田技研工業株式会社 水電解システム
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